Patent GB-678943-A (GB)
Title: Method of polymerisation and products produced thereby
IPC: C08F293/00
Filed: 1949-11-22
Abstract: Polymers of at least one compound containing in the molecule the grouping <FORM:0678943/IV (a)/1> where Z is a halogen atom or an alkyl radical, are made by polymerizing, e.g. in solution or aqueous emulsion, by heating for between 4 and 10 minutes to a temperature of at least 90 DEG  C. but below the decomposition temperature of the compound, then cooling within ten minutes to a temperature between -10 DEG  C. and 25 DEG  C. and completing the polymerization, preferably in the dark, at this lower temperature.  The polymerizable mixture may contain initially another polymerizable unsaturated compound, or the compound may be added at any later stage, e.g. when the polymerization of the compounds originally present is substantially complete.  Plasticizers, e.g. dioctyl phthalate, emulsion stabilizers, dyes, lubricants and pigments may also be added before or during the polymerization.  The polymerization may be effected in batch, continuously or semi-continuously, in the presence of catalysts, and preferably in the absence of light and molecular oxygen, e.g. the oxygen in the reaction vessel being replaced by nitrogen, methane or carbon dioxide.  Specified compounds containing the above grouping are methacrylonitrile, methyl methacrylate, 4-ethyl - 4 - pentoate, amyl - 4 - butyl - 4 - pento-ate, 4 - butyl - 4 - pentenenitrile, 5 - isopropyl-5 - hexenenitrile, 4 - isobutyl - 4 - pentenamide, 4 - amyl - 4 - pentenamide, 3 - methyl - 3-butene - 2 - one, 4 - isopropyl - 4 - pentene - 3-one, 2 - chloropropene - 1, 2 - methylbutene - 1, 2 - ethylbutene - 1, alpha - chlorostyrene, methallyl chloride, methallyl acetate, ethallyl benzoate, alpha - chloroallylcaproate, dimethallyl phthalate, 3 - methallyl - cyclohexanone, alpha - chloro - 4 - ethylstyrene, alpha - chloroacrylonitrile, butyl - 4 - chloro - 4 - pentenoate, ethyl alpha - bromoacrylate, alpha - methyl - 4-methoxystyrene, butyl alpha-chloroacrylate, 2-bromo - 1 - heptene - 3 - one, 4 - methallylbenzonitrile, 4 - chloro - 4 - pentenamide, 4-butyl - 4 - pentene - 2 - one, 4 - iodo - 4 - pentenamide, 3 - fluoro - 3 - butenenitrile, 3 - chloro-3 - butenenitrile, 5 - isopropyl - 5 - hexenenitrile, 3 - alpha - chlorovinyl - 1 - carbethoxycyclohexane, 4 - methallyl - 1 - acetoxy - benzene, 4 - carbamyl - 2 - butyl - 1 - butene, alphamethyl - vinylcyclopentane, beta - chloroallylbenzene, 4 - carboxy - 2 - chloro - 1 - pentene, 4 - methallyl - benzamide, 3 - alpha - methyl vinylcyclohexanamide, 2 - methallyl - cyclohexanecarboxamide, 7 - ethallyl - 2 - naphthamide, 7 - ethallyl - 2 - naphthonitrile, 2-alpha - ethylvinylcyclohexanenitrile, 4 - ethallyl - 2 - cyclopentanenitrile, 3 - methallylcyclopentanone, 3 - ethallyl - 1 - acetylbenzene, butyl - 2 - methyl - 2, propenoate, ethyl - 3-methyl - 3, butenoate, isobutyl - 4 - ethyl pentenoate, 2 - methyl - 2 - propenenitrile, 3-ethyl - 3 - butenenitrile, 2 - methallyl - 1-carboethoxybenzene, 3 - ethallyl - 2 - naphthamide, 5 - isopropyl - 5 - hexenenitrile, 2-methyl - 2 - propenamide, 3 - ethyl - 3 - butenamide, 3 - butyl - 3 - butenamide, 2 - methallylbenzonitrile, 3 - ethyl - butene - 2 - one, 2-methallylcyclohexanone - 5 - amyl - 5 - pentene-2 - one, 5 - ethyl - 5 - pentene - 4 - one, and mixtures.  The other polymerizable compound may be styrene, alpha methyl styrene, dichlorostyrene, vinyl naphthalene, vinyl phenol, acrylic acid, alpha-substituted acrylic acids, acrylonitrile, methacrylonitrile, methyl and propyl acrylate, methyl and butyl methacrylate, vinylidene chloride and bromide, vinyl chloride, bromide or fluoride, vinyl acetate, chloroacetate, benzoate and valerate, divinyl adipate, divinyl succinate, vinyl allyl phthalate, vinyl methallyl pimelate, diallyl phthalate, allyl acetate and diallyl succinate.  In solution the solvents may be water, cyclohexanone, cyclohexane, butane and hexane.  In aqueous emulsion the emulsifying agent may be ammonium, sodium and potassium myristates, laurates, palmitates, oleates, stearates, rosinates, and hydrobietates, sodium lauryl and potassium stearyl sulphates, sodium lauryl and potassium stearyl sulphonates, sodium cetyl sulphonate, sulphonated mineral oils, lauryl amine hydrochloride and stearyl amine hydrobromide.  Specified catalysts are benzoyl or acetyl or hydrogen or t-butyl or sodium or succinyl peroxide, persulphuric acid, peracetic acid, perphthalic acid, potassium persulphate, t-butyl perbutyrate, and di-t-butyl dipermalonate.